建立新方法 提出新观念 由后人评 ...分享 http://blog.sciencenet.cn/u/yuzh 中国科学院化学研究所

博文

我在Amazon发表的英文专著的目录

已有 2823 次阅读 2021-10-5 06:28 |系统分类:论文交流

本专著曾经在科学网连载。在去年4月, 这部专著最终在Amazon发表(ISBN: 9781655790249,简装本99美元). 感兴趣读者可以给我发信(Email地址:yuzh@iccas.ac.cn), 我可以免费提供校样本(共477页)。


《Questioning Fundamental Principles of 

Organic Chemistry》


TABLE OF CONTENTS                                                                                                            

CHAPTER 1   FUNDAMENTAL PRINCIPLES OF ORGANIC CHEMISTRY BEING

QUESTIONABLE    

Abstract                                                                                                                      1

1.1.  Introduction                                                                                                      2

1.1.1.  Fundamental Principles of Organic Chemistry                                       2

1.1.2.  Alternation of Conjugation Competition                                                4

1.2.  Experiments and Discussion                                                                            6

1.2.1.  Synthesis of 2-(N-methylamino)-anthracene                                         7

1.2.2.  Determination of Conjugated-Backbone                                                 8

1.3.  Questionable Fundamental Principles                                                             14

1.4.  Conclusions                                                                                                    16

1.5.  Reference                                                                                                        16

CHAPTER 2   ABNORMAL LARGE TWIST ANGLE OF NBA   

Abstract                                                                                                                    19

2.1.  Introduction                                                                                                    20

2.1.1.  Large Distorted Stilbene-like Species                                                   21

2.1.2.  Classic Model and Interpretations                                                         24

2.1.3.  Substituent Effect                                                                                  25

2.2.  Experimental Questioning                                                                              27

2.2.1.  Questioning Role of Non-bonded Interaction                                       27

2.2.2.  Questioning CT-2 Interaction Role                                                       29

2.3.  Theoretical Researches                                                                                   30

2.3.1.  NBA-like Species with Five-membered Ring                                       30

2.3.2.  Substituted N-benzylideneanilines                                                        35

2.4.  Conclusions                                                                                                    44

2.5.  References                                                                                                      46

CHAPTER 3   CONSTRUCTION OF FLMO BASIS SET       

Abstract                                                                                                                    52

3.0.  Forewords                                                                                                       53

3.1.  Introduction                                                                                                    57

3.2.  Constructing LFMO Basis Set                                                                       59

3.2.1.  Fragmentation of a Molecule                                                                59

3.2.2.  Sub-LFMO Basis Set for Fragment B                                                   61

3.2.3.  Superposition of Sub-basis Sets                                                            70

3.3.  Summary                                                                                                        71

3.4.  Appendix                                                                                                        71

3.5.  References                                                                                                      74

CHAPTER 4   p-DELOCALIZATION DESTABILIZATION 

Abstract                                                                                                                    79

4.1.  Introduction                                                                                                    80

4.1.1.  Morokuma Energy Decomposition                                                       80

4.1.2.  Natural Energy Decomposition Analysis                                              84

4.1.3.  Our p-s Energy Decomposition Method                                              84

4.2.  Construction of Localized States                                                                   87

4.2.1.  Construction of LFMO basis set                                                           87

4.2.2.  Construction of DSI State                                                                     89

4.2.3.  Construction of FUD State                                                                    90

4.2.4.  Construction of DSI-2 State                                                                  91

4.3. Vertical Delocalization Energy                                                                         91

4.3.1.  N-benzylideneaniline                                                                            91

4.3.2.  Heterocyclic NBA-like Species                                                            97

4.3.3.  Substituted NBAs                                                                                  99

4.4.  Summary                                                                                                      105

4.5.  Appendix                                                                                                      106

4.6.  References                                                                                                    112

CHAPTER 5   ELECTRON DELOCALIZATION DESTABILIZATION  

Abstract                                                                                                                  115

5.1.  NBO Method                                                                                                116

5.1.1.  NBO Basis Set                                                                                     116

5.1.2.  NBO Vertical Delocalization Energy                                                  119

5.1.3.  Localization Degree of LMO Basis Set.                                             120

5.2.  p-delocalization Indeed Destabilization                                                       126

5.2.1.  Basic Flaws of NBO                                                                            127

5.2.2.  Deleting Hartree-Fock Exchange                                                        131

5.3.  Destabilizing p-s Interaction                                                                       137

5.3.1.  N-benzylideneaniline                                                                          137

5.3.2.  NBA-like Species                                                                                141

5.4.  Destabilizing Non-bonded s-s Interaction                                                  143

5.4.1.  Construction of FUL State                                                                  144

5.4.2.  Reasonable STO-3G Basis Set                                                            145

5.4.3.  Construction of PDSI Electronic State                                                145

5.4.4.  Non-bonded s-s Interaction                                                               147

5.4.5.  s-s Interaction Distorting Molecule.                                                  148

5.5.  Summary                                                                                                      151

5.6.  Appendix                                                                                                      153

5.7.  References                                                                                                    159

CHAPTER 6   RESTRICTED GEOMETRY OPTIMIZATION        

Abstract                                                                                                                  161

6.0.  Forewords                                                                                                     162

6.0.1.  So-called Evidence of Conjugation Stabilization                               162

6.0.2.  Benzene and Aromaticity                                                                    165

6.1.  Our 2007 Method                                                                                         169

6.1.1.  Program of Localizing Geometry                                                        170

6.1.2.  A New Type of Additive Energy Effect                                             174

6.1.3.  Extra Stabilization Energy of Benzene                                               177

6.2.  ESEs for Benzene-like Species                                                                    180

6.2.1.  Aza-1,3,5-Hexatrienes                                                                         181

6.2.2.  Benzene-like Species                                                                          182

6.2.3.  Furan-like Species                                                                               184

6.3.  Substituted Benzenes                                                                                   189

6.3.1.  Extra Stabilization Energy                                                                  190

6.3.2.  Extra Stabilization Energy of Parent Benzene Ring                           194

6.3.3.  Pure Conjugation Effect                                                                      194

6.3.4.  Pure Inductive Effect                                                                           195

6.3.5. Conjugation and Inductive Effect                                                          195

6.3.6.  Substituent Effect Always Distortive                                                  195

6.4.  Conclusions                                                                                                  198

6.5.  Appendix                                                                                                      198

6.6.  References                                                                                                    203

CHAPTER 7   POLYCYCLIC BENZENOID HYDROCARBONS

Abstract                                                                                                                  208

7.0. Forewords                                                                                                        209

7.0.1.  Estimation of Resonance Energy                                                        209

7.0.2.  Calculation of Electron Delocalization Energy                                   210

7.0.3.  Randić and Plavsić method                                                                 212

7.1.  Method                                                                                                         215

7.1.1.  GL Geometry of Phenanthrene                                                           215

7.1.2.  GE-m Geometries of Phenanthrene                                                    215

7.1.3.  Substituted 1,1-dibutadienyl-ethylene                                                 218

7.1.4.  ESE of Phenanthrene                                                                           219

7.1.5.  Corrected ESE of Phenanthrene                                                          219

7.2.  Acenes                                                                                                          219

7.2.1.  Generalized Definition of Fusion Bond                                              220

7.2.2.  Fusion Double Bond                                                                            223

7.2.3.  ESE and CESE                                                                                    223

7.2.4.  Energy Effect Increments                                                                    225

7.3.  Position Rule and Energy Rule                                                                    230

7.4.  Dibenzoacenes                                                                                              231

7.4.1.  Naphtho[2.3-e]pyrene                                                                         231

7.4.2.  GL Sextet Rule                                                                                    237

7.5.  Conclusions                                                                                                  242

7.6.  References                                                                                                    243

CHAPTER 8   NEW METHOD TO LOCALIZE p-ELECTRONS        

Abstract                                                                                                                  245

8.0. Forewords                                                                                                        246

8.0.1.  Historical Roles of Cyclobutadiene                                                    246

8.0.2.  4n+2 Rule                                                                                            247

8.0.3.  Kollma Method and Jug Method                                                         248

8.0.4.  Fundamental Flaws of BLW Method                                                  249

8.1.  Introduction                                                                                                  251

8.1.1.  Our 2007 Method Needing Improvement                                           251

8.1.2.  p-s Energy Decomposition                                                                 253

8.1.3.  Two-electron Exchange Integrals                                                       256

8.1.4.  MPn Correlation Energy                                                                     257

8.1.5.  Evidences for Role of HF-EX                                                             258

8.2.  Our 2011 Method                                                                                         259

8.2.1.  Versions of Our 2011 Method                                                             260

8.2.2.  Reliable Our 2011 Method                                                                  263

8.3.  Extra Stabilization Energy of Benzene                                                        267

8.3.1.  Hartree-Fock Exchange Effects                                                          267

8.3.2.  More Reasonable Our 2011 Method                                                   269

8.4.  Vertical Delocalization Energy                                                                    273

8.5.  Cyclobutadiene                                                                                             274

8.6.  Conclusions                                                                                                  275

8.7.  Appendix                                                                                                      275

8.8.  References                                                                                                    279

CHAPTER 9   [N]ANNULENES AND PBHS 

Abstract                                                                                                                  282

9.1.  Introduction                                                                                                  283

9.1.1.  [4n+2] Rule Not Always a Truth                                                        284

9.1.2Driving Force for Distorting Ring                                                        285

9.2.  p-s Energy Decomposition                                                                          286

9.2.1.  DFT Molecular Energy                                                                       286

9.2.2.  MPn Molecular Energy                                                                       288

9.3.  Benzene                                                                                                        289

9.3.1.  Three Distortion Models                                                                     289

9.3.2.  BLE Leading to Minimization of Nuclear Repulsion                          291

9.4.  [N]Annulenes                                                                                               294

9.4.1.  Meaning of Symbol “[16]-54444”                                                      295

9.4.2.  Relationship between Configuration and VDE                                   296

9.4.3.  Possible Configuration Isomers of a [N]Annulene                             297

9.4.4.  Vertical Delocalization Energies                                                         302

9.4.5.  Extra Stabilization Energy                                                                  306

9.5. PBHs                                                                                                                311

9.5.1.  Phenanthrene                                                                                       311

9.5.2.  Acenes, Triphenylene and Chrysene                                                   314

9.6.  Conclusions                                                                                                  317

9.7.  References                                                                                                    317

CHAPTER 10   STRAINED-AROMATIC MOLECULES - p-DISTORTIVITY

Abstract                                                                                                                  321

10.0.  Forewords                                                                                                   322

10.0.1.  Mulliken’s Model of Charge Transfer Complex                               323

10.0.2.  Our Energy Decomposition Methods                                                323

10.0.3.  Thermodynamic Mechanism of Reaction NH3 + BH3                      328

10.1.  Introduction                                                                                                338

10.1.1.  Mills-Nixon Effect.                                                                           341

10.1.2.  Experimental Probe for p-Interaction Role                                       344

10.2.  Eliminating p-Interaction                                                                           345

10.2.1.  Construction of PLG                                                                         345

10.2.2.  p-Delocalization Causing BLA                                                         346

10.2.3.  Energy Decomposition                                                                      348

10.3.  Universality of p-Distortivity                                                                     351

10.3.1.  Comparison of Dr(PLG) and Dr(G)                                                  351

10.3.2.  dDr(GP) versus DE(GP)                                                                    353

10.3.3.  Large Differences between C6B6H6 and C6N6H6                               357

10.4.  Forces Acting on Ring Bonds                                                                    360

10.4.1.  Endocyclic Bonds                                                                              364

10.4.2.  Exocyclic Bonds                                                                                365

10.5.  C6B6 and C6N3H3                                                                                        368

10.5.1.  Bond Angle                                                                                       368

10.5.2.  Bond Length                                                                                      369

10.6.  Secondary Structural Effects                                                                      369

10.7.  Conclusions                                                                                                370

10.8.  References                                                                                                  372

CHAPTER 11   STRAINED-AROMATIC MOLECULES - ESE 

Abstract                                                                                                                  376

11.1.  Introduction                                                                                                377

11.2.  Benzotricyclobutadiene                                                                              378

11.2.1.  ESE of Whole Molecule                                                                    380

11.2.2.  ESE of Central Ring                                                                          384

11.3.  Strained-Aromatic Molecules                                                                    387

11.3.1.  C6X6H6 and C6X3H3 (X = B, Al, Ga)                                                387

11.3.2.  C6X6H6 (X = N, P, As, Si, Ge)                                                          388

11.3.3.  C6X3H3 (X = N, P, As)                                                                      389

11.3.4.  C6X6 (X = B, N, P, As)                                                                      390

11.4.  ESE versus Dr(G)                                                                                       391

11.4.1.  Molecules with Dr(G) > 0                                                                 391

11.4.2.  Molecules with Dr(G) < 0                                                                 395

11.5.  Conclusions                                                                                                396

11.6.  References                                                                                                  397

CHAPTER 12   LOCALIZED GEOMETRY OPTIMIZATION 

Abstract                                                                                                                  398

12.1.  Introduction                                                                                                399

12.1.1.  Pauling's Resonance Theory                                                             399

12.1.2.  Coulson's Method                                                                              402

12.1.3.  Dewar’s Viewpoint of Hybridization                                                403

12.1.4.  Covalent Radii                                                                                   403

12.1.5.  Controversy over Resonance Existence                                            405

12.1.6.  Historical Limitations                                                                        406

12.2.  Development of Our Method                                                                     407

12.2.1.  Our 2007 Method                                                                              407

12.2.2.  Our 2011 Method                                                                              411

12.3.  Our 2014 Method                                                                                       413

12.3.1.  More Reasonable than Our 2011 Method                                         413

12.4.  Butadiene Derivatives                                                                                423

12.4.1.  Localized GL Geometries                                                                 424

12.4.2.  Adjacent Conjugation and Transmission                                          433

12.5.  Conclusions                                                                                                442

12.6.  References                                                                                                  444




https://blog.sciencenet.cn/blog-94786-1306778.html

上一篇:第五章(四)Formally Refuting the Maksić’s Comment (全文)
收藏 IP: 115.171.63.*| 热度|

2 池德龙 杨正瓴

该博文允许注册用户评论 请点击登录 评论 (1 个评论)

数据加载中...

Archiver|手机版|科学网 ( 京ICP备07017567号-12 )

GMT+8, 2024-12-14 17:48

Powered by ScienceNet.cn

Copyright © 2007- 中国科学报社

返回顶部